US5039815A - 1-halo-azolylethane derivatives and fungicides containing them - Google Patents
1-halo-azolylethane derivatives and fungicides containing them Download PDFInfo
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- US5039815A US5039815A US07/564,783 US56478390A US5039815A US 5039815 A US5039815 A US 5039815A US 56478390 A US56478390 A US 56478390A US 5039815 A US5039815 A US 5039815A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Definitions
- the present invention relates to new haloazole compounds, processes for their manufacture, and fungicides containing them.
- R 1 and R 2 are C 1 -C 8 -alkenyl phenyl, biphenyl, naphthyl, benzyl, C 3 -C 9 -cycloalkyl or C 3 -C 8 -cycloalkenyl, each of which is unsubstituted or substituted by halogen, nitro, phenoxy, alkyl, alkoxy, amino or haloalkyl, each of 1 to 4 carbon atoms,
- n is an integer from 1 to 5, or 0,
- E is Cl or Br
- X is CH or N
- the compounds of the formula I contain asymmetric carbon atoms amd may therefore occur as enantiomers and diastereomers.
- the invention encompasses both the pure isomers and mixtures of them.
- the diastereomer mixtures may be separated into their components by conventional methods, for example by fractional crystallization or by chromatography on silica gel.
- the racemates may be separated by conventional methods, for instance by formation of a salt with an optically active acid, separation of the diastereomeric salts and liberation of the enantiomers with the aid of a base.
- R 1 and R 2 are identical or different and denote for example: methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, neopentyl, hexyl, octyl, trifluoromethyl, trichloromethyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 3-bromophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-ch
- n denotes 0, 1, 2, 3, 4 or 5.
- acid addition salts are the hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfonates.
- the anion is as a rule unimportant.
- the active ingredient salts according to the invention are produced by reacting the 1-halo-1-azolylethane derivatives I with the acids.
- Metal salts of active ingredients I, or of their salts, may be formed with copper, zinc, tin, manganese, iron, cobalt or nickel by reacting the 1-halo-1-azolylethane derivatives with appropriate metal salts, e.g..
- the compounds of the formula I may be prepared for instance by reacting a compound of the formula II ##STR3## where R 1 , R 2 and n have the above meanings, with a compound of the formula III ##STR4## where X has the above meanings, in the presence of corresponding thionyl halides. The reaction is carried out at from -30° to 80° C. in the presence or absence of a solvent or diluent.
- Preferred solvents and diluents are nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane and diisopropyl ether, and in particular hydrocarbons and chlorohydrocarbons such as pentane, hexane, toluene, methylene chloride, chloroform, carbon tetrachloride and dichloroethane and appropriate mixtures thereof.
- the compounds of the formula lI may be prepared in accordance with generally known aldehyde synthesis methods (Houben-Weyl-Muller, Methoden der organischen Chemie, Georg-Thieme-verlag, Stuttgart 1983, Vol. E 3. The following example illustrates the manufacture of the active ingredients.
- novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides.
- the fungicidal compounds are of Particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
- the novel compounds are particularly useful for controlling the following plant diseases:
- Botrytis cinerea (gray mold) in strawberries and grapes
- the compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
- novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
- the application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient.
- the formulations are produced in known manner, of example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents.
- auxiliaries for this purpose are solvents such as aromatics (e.g., xylene, chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone, amines (e.g., ethanolamine, dimethylformamide, and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g..).
- solvents such as aromatics (e.g., xylene, chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone, amines (e.g., ethanolamine, dimethylformamide, and water;
- fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90 wt% of active ingredient.
- the application rates are from 0.2 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired.
- novel compounds may also be used for protecting materials, for example against Paecilomyces variotii.
- agents and the ready-to-use formulations prepared from them are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
- formulations are given below.
- I. 90 parts by weight of compound no. 74 is mixed with 10 parts by weight of N-methyl- ⁇ -pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
- 89 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-Nmonoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 Parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
- 94 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel.
- a formulation of the active ingredient is obtained having good adherence.
- VIII. 40 parts by weight of compound no. 116 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
- lX 20 parts by weight of compound no.
- the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum.
- the following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
- fungicides which may be combined with the novel compounds are:
- heterocyclic substances such as
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1-Halo-1-azolylethane derivatives of the formula I ##STR1## where R1 and R2 are C1 -C8 -alkyl, phenyl, biphenyl, naphthyl, benzyl, C3 -C8 -cycloalkyl or C3 -C8 -cycloalkenyl, each of which is unsubstituted or substituted,
n is an integer from 1 to 5, or 0,
E is Cl or Br, and
X is CH or N,
their plant-tolerated acid addition salts and metal complexes, and fungicides containing these compounds.
Description
This is a division of application Ser. No. 07/363,773, filed on June 9, 1989, now abandoned.
The present invention relates to new haloazole compounds, processes for their manufacture, and fungicides containing them.
The use of 1-(1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-pentane as a fungicide has been disclosed (Thomson, Agricultural Chemicals, Book IV, Fungicides, page 124, 1988).
We have now found that 1-halo-1-azolylethane derivatives of the general formula I ##STR2## where R1 and R2 are C1 -C8 -alkenyl phenyl, biphenyl, naphthyl, benzyl, C3 -C9 -cycloalkyl or C3 -C8 -cycloalkenyl, each of which is unsubstituted or substituted by halogen, nitro, phenoxy, alkyl, alkoxy, amino or haloalkyl, each of 1 to 4 carbon atoms,
n is an integer from 1 to 5, or 0,
E is Cl or Br, and
X is CH or N,
and their plant-tolerated acid addition salts and metal complexes, have a better fungicidal action, especially on cereal diseases, than the prior art azole compounds.
The compounds of the formula I contain asymmetric carbon atoms amd may therefore occur as enantiomers and diastereomers. The invention encompasses both the pure isomers and mixtures of them. The diastereomer mixtures may be separated into their components by conventional methods, for example by fractional crystallization or by chromatography on silica gel. The racemates may be separated by conventional methods, for instance by formation of a salt with an optically active acid, separation of the diastereomeric salts and liberation of the enantiomers with the aid of a base.
Both the individual enantiomers and diastereomers, and mixtures thereof may be used as fungicidal active ingredients. R1 and R2 are identical or different and denote for example: methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, neopentyl, hexyl, octyl, trifluoromethyl, trichloromethyl, phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-bromophenyl, 3-chlorophenyl, 3-bromophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2,4-dichlorophenyl, 2,3-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2-chloro-6-fluorophenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 4-ethylphenyl, 4-isopropropylphenyl, 4-tert.-butylphenyl, 4-tert.-butyloxyphenyl, 2-chloro-4-fluorophenyl, 2chlor-6-methylphenyl, 3,4-dimethoxyphenyl, 3-phenoxyphenyl, 4-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-aminophenyl, 4-aminophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, C6 -cycloalkenyl, 2-cyclohexenyl, 3-cyclohexenyl and norbornyl. n denotes 0, 1, 2, 3, 4 or 5. Examples of acid addition salts are the hydrochlorides, bromides, sulfates, nitrates, phosphates, oxalates and dodecylbenzenesulfonates. As the action of the salts is attributable to the cation, the anion is as a rule unimportant. The active ingredient salts according to the invention are produced by reacting the 1-halo-1-azolylethane derivatives I with the acids. Metal salts of active ingredients I, or of their salts, may be formed with copper, zinc, tin, manganese, iron, cobalt or nickel by reacting the 1-halo-1-azolylethane derivatives with appropriate metal salts, e.g.. copper sulfate, zinc chloride and tin chloride. The compounds of the formula I may be prepared for instance by reacting a compound of the formula II ##STR3## where R1, R2 and n have the above meanings, with a compound of the formula III ##STR4## where X has the above meanings, in the presence of corresponding thionyl halides. The reaction is carried out at from -30° to 80° C. in the presence or absence of a solvent or diluent. Preferred solvents and diluents are nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, diethyl ether, dimethoxyethane, dioxane and diisopropyl ether, and in particular hydrocarbons and chlorohydrocarbons such as pentane, hexane, toluene, methylene chloride, chloroform, carbon tetrachloride and dichloroethane and appropriate mixtures thereof. The compounds of the formula lI may be prepared in accordance with generally known aldehyde synthesis methods (Houben-Weyl-Muller, Methoden der organischen Chemie, Georg-Thieme-verlag, Stuttgart 1983, Vol. E 3. The following example illustrates the manufacture of the active ingredients.
At 0° C., 13.1 g of thionyl chloride is added to a solution of 15.222 g of 1,2,4-triazole in 150 ml of methylene choride. After all has been added, the mixture is stirred for 30 minutes at room temperature (20° C.): subsequently, 15.5 g of 2,3-biphenylpropanal is added. After the mixture has been stirred at room temperature for 12 to 15 hours, 100 ml of water is added and the organic phase separated off. The aqueous phase which remains is extracted by shaking twice with methylene chloride, and the collected organic phases are washed twice with saturated sodium bicarbonate solution. The isolated organic phase -s then dried over sodium sulfate and concentrated. There is obtained 30.0 g (92%) of 1-chloro-1-(1,2,4-triazol-1-yl-)2,3-diphenylpropane. The compounds listed in the table below may be obtained analogously to Example 1:
TABLE
__________________________________________________________________________
##STR5##
__________________________________________________________________________
Ex.
R.sup.1 R.sup.2 n E X D1:D2*
IR (cm.sup.-1)
__________________________________________________________________________
1 C.sub.6 H.sub.5
C.sub.6 H.sub.5
1 Cl
N 4:1 1506,1497,1275,1135,762,699
2 C.sub.6 H.sub.5
4-FC.sub.6 H.sub.4
1 Cl
N -- --
3 C.sub.6 H.sub.5
2-FC.sub.6 H.sub.4
1 Cl
N -- --
4 C.sub.6 H.sub.5
2-ClC.sub.6 H.sub.4
1 Cl
N -- --
5 C.sub.6 H.sub.5
4-ClC.sub.6 H.sub.4
1 Cl
N -- --
6 C.sub.6 H.sub.5
2,4-Cl.sub.2C.sub.6 H.sub.3
1 Cl
N -- --
7 C.sub.6 H.sub.5
2,4-Cl.sub.2C.sub.6 H.sub.3
1 Cl
CH -- --
8 C.sub.6 H.sub.5
C.sub.10 H.sub.7
1 Cl
N -- --
9 C.sub.6 H.sub.5
CH.sub.3 1 Cl
N -- --
10 C.sub.6 H.sub.5
C.sub.4 H.sub.9
1 Cl
N -- --
11 C.sub.6 H.sub.5
cyclohexyl 1 Cl
N -- --
12 C.sub.6 H.sub.5
C.sub.6 H.sub.5
0 Cl
N 1:1 1506,1499,1275,1134,742,703
13 C.sub.6 H.sub.5
4-FC.sub.6 H.sub.5
0 Cl
N -- --
14 C.sub.6 H.sub.5
2-ClC.sub.6 H.sub.5
0 Cl
N -- --
15 C.sub.6 H.sub.5
C.sub.12 H.sub.9
0 Cl
N -- --
16 C.sub.6 H.sub.5
cyclohexyl 0 Cl
N 1:1 2927,2854,1505,1450,1275,1135,703
17 C.sub.6 H.sub.5
3-cyclohexenyl
0 Cl
N -- --
18 C.sub.6 H.sub.5
C.sub.6 H.sub.5
2 Cl
N 3:1 1506,1496,1276,1135,750,700
19 C.sub.6 H.sub.5
4-FC.sub.6 H.sub.5
2 Cl
N -- --
20 C.sub.6 H.sub.5
2-ClC.sub.6 H.sub.5
2 Cl
N -- --
21 C.sub.6 H.sub.5
C.sub.6 H.sub.5
3 Cl
N -- --
22 C.sub.6 H.sub.5
4-ClC.sub.6 H.sub.4
3 Cl
N -- --
23 4-FC.sub.6 H.sub.4
C.sub.6 H.sub.5
0 Cl
N -- --
24 4-FC.sub.6 H.sub.4
4-FC.sub.6 H.sub.4
0 Cl
N -- 1508,1229,1160,837
25 4-FC.sub.6 H.sub.4
2-FC.sub.6 H.sub.4
0 Cl
N 1:1 1510,1493,1276,1233,809,756
26 4-FC.sub.6 H.sub.4
2-ClC.sub.6 H.sub.4
0 Cl
N -- --
27 4-FC.sub.6 H.sub.4
4-ClC.sub.6 H.sub.4
0 Cl
N -- --
28 4-FC.sub.6 H.sub.4
2,4-Cl.sub.2C.sub.6 H.sub.3
0 Cl
N -- --
29 4-FC.sub.6 H.sub.4
4-OCH.sub.3C.sub.6 H.sub.4
0 Cl
N -- --
30 4-FC.sub.6 H.sub.4
iso-C.sub.3 H.sub.7
0 Cl
N 7:3 2959,1510,1275,1229,1136,841
31 4-FC.sub.6 H.sub.4
2-FC.sub.6 H.sub.4
1 Cl
N -- --
32 4-FC.sub.6 H.sub.4
4-FC.sub.6 H.sub.4
2 Cl
N -- --
33 2-ClC.sub.6 H.sub.4
4-FC.sub.6 H.sub.4
0 Cl
N -- --
34 2-ClC.sub.6 H.sub.4
4-ClC.sub.6 H.sub.4
0 Cl
N -- --
35 2-ClC.sub.6 H.sub.4
2,4-Cl.sub.2C.sub.6 H.sub.3
1 Cl
N -- --
36 2-ClC.sub.6 H.sub.4
CH.sub.3 1 Cl
N -- --
37 2-ClC.sub.6 H.sub.4
CH.sub.3 2 Cl
N 1:1 2960,1506,1275,1135,753
38 4-ClC.sub.6 H.sub.4
4-ClC.sub.6 H.sub.4
0 Cl
N -- --
39 4-ClC.sub.6 H.sub.4
4-FC.sub.6 H.sub.4
1 Cl
N -- --
40 4-ClC.sub.6 H.sub.4
CH.sub.3 1 Cl
N -- --
41 4-ClC.sub.6 H.sub.4
CH.sub.3 2 Cl
N 2:1 resin
42 2,4-Cl.sub.2C.sub.6 H.sub.3
4-FC.sub.6 H.sub.4
0 Cl
N -- --
43 2,4-Cl.sub.2C.sub.6 H.sub.3
2-ClC.sub.6 H.sub.4
0 Cl
N -- --
44 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 1 Cl
N 1.2:1
2970,1506,1476,1275,1199,1135,805
45 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 2 Cl
N 1:1 2961,1506,1475,1275,1199,1135,797
46 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 3 Cl
N 9:1 2958,1506,1475,1275,1135,804
47 cyclohexyl
4-FC.sub.6 H.sub.4
1 Cl
N -- --
48 cyclohexyl
2-ClC.sub.6 H.sub.4
1 Cl
N -- --
49 cyclohexyl
2,4-Cl.sub.2C.sub.6 H.sub.3
1 Cl
N -- --
50 cyclohexyl
2-ClC.sub.6 H.sub.4
2 Cl
N -- --
51 CH.sub.3 4-FC.sub.6 H.sub.4
0 Cl
N -- --
52 CH.sub.3 2-ClC.sub.6 H.sub.4
0 Cl
N -- --
53 CH.sub.3 4-ClC.sub.6 H.sub.4
1 Cl
N 1:1 1506,1492,1275,1136,1015,811
54 CH.sub.3 4-FC.sub.6 H.sub.4
1 Cl
N 2:1 1511,1276,1223,1136,838
55 CH.sub.3
##STR6## 1 Cl
N 1:1 2961,2934,1508,1276,1136,1004,818
56 CH.sub.3
##STR7## 1 Cl
N -- --
57 CH.sub.3
##STR8## 1 Cl
N 2:1 1514,1275,1255,1033,833,768
58 CH.sub.3
##STR9## 1 Cl
N 1:1 2979,1611,1511,1275,1248,1047
59 CH.sub.3
##STR10## 1 Cl
N 1:1 2966,1611,1511,1275,1250,1135
60 CH.sub.3 4-NO.sub.2C.sub.6 H.sub.4
2 Cl
N -- --
61 CH.sub.3 2-FC.sub.6 H.sub.4
3 Cl
N -- --
62 CH.sub.3 CH(C.sub.6 H.sub.5).sub.2
0 Cl
N 1:1 1496,1451,1277,1137,748,705
63 tert.-butyl
4-ClC.sub.6 H.sub.4
0 Cl
N -- --
64 tert.-butyl
4-FC.sub.6 H.sub.4
0 Cl
N -- --
__________________________________________________________________________
Ex.
R.sup.1 R.sup.2 n E X D1:D2*
IR (cm.sup.-1)/m.p.
__________________________________________________________________________
65 tert.-butyl
2-ClC.sub.6 H.sub.4
0 Cl
N -- --
66 tert.-butyl
2,4-Cl.sub.2C.sub.6 H.sub.3
0 Cl
N -- --
67 tert.-butyl
4-ClC.sub.6 H.sub.4
1 Cl
N -- --
68 tert.-butyl
4-FC.sub.6 H.sub.4
1 Cl
N -- --
69 tert.-butyl
4-ClC.sub.6 H.sub.4
2 Cl
N -- --
70 tert.-butyl
4-ClC.sub. 6 H.sub.4
3 Cl
N -- --
71 tert.-butyl
cyclohexyl 0 Cl
N -- --
72 tert.-butyl
cyclohexyl 1 Cl
N -- --
73 tert.-butyl
cyclohexyl 1 Cl
N -- --
74 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 1 Cl
CH 1:1 82-88°
75 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 2 Cl
CH 1:1 78-82°
76 C.sub.6 H.sub.5
C.sub.6 H.sub.5
0 Br
N -- --
77 C.sub.6 H.sub.5
C.sub.6 H.sub.5
1 Br
N 1:1 1506,1497,1454,1274,1133,700
78 C.sub.6 H.sub.5
C.sub.6 H.sub.5
2 Br
N -- --
79 C.sub.6 H.sub.5
cyclohexyl 0 Br
N -- --
80 4-FC.sub.6 H.sub.4
iso-C.sub.3 H.sub.7
0 Br
N -- --
81 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 1 Br
N -- --
82 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 2 Br
N 1:1 2961,2935,1506,1475,1274,1133,823
83 CH.sub.3 4-FC.sub.6 H.sub.4
0 Br
N -- --
84 CH.sub.3
##STR11## 1 Br
N 1:1 2963,2933,2507,1421,1274,1134,817
85 CH.sub.3
##STR12## 1 Br
N 1:1 2979,1611,1511,1249,1047
86 CH.sub.3
##STR13## 1 Br
N 1:1 2965,1611,1511,1250,1134
87 CH.sub.3 CH(C.sub.6 H.sub.5).sub.2
0 Br
N -- --
88 C(CH.sub.3).sub.3
4-ClC.sub.6 H.sub.4
0 Br
N -- --
89 C.sub.6 H.sub.5
CH.sub.3 0 Cl
N 3:1 resin
90 C.sub.6 H.sub.5
CH.sub.3 2 Cl
N 3:1 2960,1506,1275,1135,700
91 C.sub.6 H.sub.5
CH.sub.3 2 Cl
CH 1,2:1
2959,1229,1153,1088,754
92 4-FC.sub.6 H.sub.4
CH.sub.3 3 Cl
N 2:1 2958,1510,1276,1226,840
93 4-ClC.sub.6 H.sub.4
C.sub.2 H.sub.5
5 Cl
N 2:1 2927,1505,1492,1275,1135,1015
94 4-FC.sub.6 H.sub.4
2-FC.sub.6 H.sub.4
0 Cl
CH 1:1 1511,1491,1230,1078,807,756
95 4-ClC.sub.6 H.sub.4
CH.sub.3 0 Cl
N 3:1 1506,1495,1275,1135,1015,836,777
96 4-ClC.sub.6 H.sub.4
CH.sub.3 2 Cl
CH 2:1 2960,1492,1092,1015,778
97 4-ClC.sub.6 H.sub. 4
CH.sub.3 5 Cl
N 2:1 2929,1506,1492,1275,1135,1015,765
98 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 2 Cl
N 2:1 2958,1506,1475,1275,1135,804
99 2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 2 Cl
CH 3:7 2957,1489,1478,1226,1076,802
100
2-ClC.sub.6 H.sub.4
CH.sub.3 5 Cl
CH 2:1 resin
101
3-ClC.sub.6 H.sub.4
CH.sub.3 2 Cl
N 1:1 2961,1506,1275,1135,1001,767
102
3,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 1 Cl
N 1:1 1506,1472,1275,1134,778,776
103
4-ClC.sub.6 H.sub.4
2-ClC.sub.6 H.sub.4
0 Cl
N 1:1 1506,1493,1275,1133,1015,754
104
4-ClC.sub.6 H.sub.4
2-ClC.sub.6 H.sub.4
0 Cl
CH 1:1 1492,1227,1091,1015,754,736
105
2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 5 Cl
N 1:1 1506,1475,1275,1135,801,791
106
2,4-Cl.sub.2C.sub.6 H.sub.3
C.sub.3 H.sub.7
5 Cl
N 1:1 2926,1505,1475,1275,1134,825
107
2-ClC.sub.6 H.sub.4
C.sub.2 H.sub.5
5 Cl
N 1:1 2927,1505,1275,1135,752
108
4-C.sub.6 H.sub.5 OC.sub.6 H.sub.4
CH.sub.3 5 Cl
N 7:2 2929,1506,1489,1241,872
109
4-C.sub.6 H.sub.5 OC.sub.6 H.sub.4
CH.sub.3 1 Cl
N 2:1 1589,1506,1489,1239,872
__________________________________________________________________________
Ex.
R.sup.1 R.sup.2 n E X D1:D2*
IR (cm.sup.-1)
__________________________________________________________________________
110
2-naphthyl
CH.sub.3 1 Cl
N 1.2:1
1506,1275,1135,780
111
2-naphthyl
CH.sub.3 3 Cl
N 1:1 2957,1506,1275,1135,778
112
2-naphthyl
CH.sub.3 5 Cl
N 1:1 2928,1506,1275,1135,777
113
p-C.sub.6 H.sub.5C.sub.6 H.sub.4
CH.sub.3 1 Cl
N -- --
114
4-FC.sub.6 H.sub.4
C.sub.3 H.sub.7
5 Cl
N 1:1 2927,1510,1276,1226,1135,840
115
2,4-Cl.sub.2C.sub.6 H.sub.3
CH.sub.3 3 Cl
CH 2:1 resin
116
CH.sub.3 4-OCH.sub.3C.sub.6 H.sub.4
1 Cl
N 3:1 1512,1250,1035,819
117
4-FC.sub.6 H.sub.4
2-ClC.sub.6 H.sub.4
0 Cl
N 1:1 1509,1276,1233,1059,808,750
118
4-FC.sub.6 H.sub.4
2-ClC.sub.6 H.sub.4
0 Cl
CH 1:1 resin
119
4-FC.sub.6 H.sub.4
C.sub.6 H.sub.4
0 Cl
N 1:1 1510,1276,1227,1135,809,732
120
4-FC.sub.6 H.sub.4
C.sub.6 H.sub.4
0 Cl
CH 1:1 1602,1510,1496,1228,813,730
121
4-FC.sub.6 H.sub.4
4-ClC.sub.6 H.sub.4
0 Cl
N -- 112° C.
__________________________________________________________________________
*Ratio of the diastereomers obtained
In general terms the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the Ascomycetes and Basidiomycetes classes. Some of them have a systemic action and can be used as foliar and soil fungicides. The fungicidal compounds are of Particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits. The novel compounds are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
Podosphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
Rhizoctonia species in cotton and lawns,
Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples,
Helminthosporium species in cereals,
Septoria nodorum in wheat,
Botrytis cinerea (gray mold) in strawberries and grapes,
Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes,
Fusarium and verticillium species in various plants,
Plasmopara viticola in grapes,
Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, of example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene, chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone, amines (e.g., ethanolamine, dimethylformamide, and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g.. highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose. The fungicidal agents generally contain from 0.1 to 95, and preferably from 0.5 to 90 wt% of active ingredient. The application rates are from 0.2 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, for example against Paecilomyces variotii. The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering. Examples of formulations are given below. I. 90 parts by weight of compound no. 74 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops. II. 20 parts by weight of compound no. 89 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-Nmonoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 Parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained. III. 20 parts by weight of compound no. 94 is dissolved in a mixture consisting of 40 Parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 116 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 Parts by weight of a mineral oil fraction-having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained. V. 80 parts by weight of compound no. 74 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained. VI. 3 parts by weight of compound no. 89 is intimately mixed with 97 Parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient. VII. 30 parts by weight of compound no. 94 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence. VIII. 40 parts by weight of compound no. 116 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion. lX. 20 parts by weight of compound no. 74 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained. In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in an increase in the fungicidal spectrum. The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
Examples of fungicides which may be combined with the novel compounds are:
sulfur,
dithiocarbamates and the-r derivatives, such as
ferric dimethyldithiocarbamate,
zinc dimethyldithiocarbamate,
zinc ethylenebisdithiocarbamate,
manganese ethylenebisdithiocarbamate,
manganese zinc ethylenediaminebisdithiocarbamate,
tetramethylthiuram disulfides,
ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,
ammonia complex of zinc N,N'-propylenebisdithiocarbamate,
zinc N,N'-propylenebisdithiocarbamate and
N,N'-polypropylenebisthiocarbamyl disulfide;
nitro derivatives, such as
dinitro(1-methylheptyl)-phenyl crotonate,
2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and
diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as
2-heptadecylimidazol-2-yl acetate,
2,4-dichloro-6-(o-chloroanilino)-s-triazine,
0,0-diethyl phthalimidophosphonothioate,
5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithio[4,5-b]quinoxaline,
methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,
2-methoxycarbonylaminobenzimidazole,
2-(fur-2-yl)-benzimidazole,
2-(thiazoi-4-yl)benzimidazole,
N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,
N-trichloromethylthiotetrahydrophthalimide,
N-trichloromethylthiophthalimide,
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-thiocyanatomethylthiobenzothiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,
2-thiopyridine 1-oxide,
8-hydroxyquinoline and its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,
2-methylfuran-3-carboxanilide,
3 2,5-dimethylfuran-3-carboxanilide,
2,4,5-trimethylfuran-3-carboxanilide,
2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,
N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,
2-methylbenzanilide,
2-iodobenzanilide,
N-formyl-N-morpholine-2,2,2-trichloroethylacetal,
piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),
1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecylmorpholine and its salts,
2,6-dimethyl-N-cyclododecylmorpholine and its salts,
N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,
N-[3-p-tert.-butylphenyl)-2-methylpropyl]-piperidine,
1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4triazole,
1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,
N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,
1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,
α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,
5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,
bis-(p-chlorophenyl-3-pyridinemethanol,
1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,
1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,
and various fungicides, such as
dodecylguanidine acetate,
3-[3-(3,5-dimethyl-2-oxycyclohexyl-2-hydroxyethyl)-glutaramide, hexachlorobenzene.
DL-methyl-N-(2,6-dimethylphenyl-N-fur-2-yl alanate,
methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,
N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,
5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,
3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,
3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,
N-(3.5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,
2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,
1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,
2,4-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,
N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and
1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.
The compound 1-(1,2,4-triazol-1-yl)-2-(2-(2,4-dichlorophenyl)-pentane (A) disclosed in Thomson, Agricultural Chemicals, Book IV, Fungicides, page 124, 1988. was used for comparison purposes. Action on Botrytis cinerea in pimientos
Pimiento seedlings of the "Neusiedler Ideal Elite" variety with 4 to 5 well developed leaves were sprayed to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were sprayed with a conidial suspension of the fungus Botrytis cinerea and kept in a highhumidity chamber at 22 to 24° C. After 5 days, the disease had spread on the untreated control plants to such an extent that the necroses covered the major portion of the leaves. The results show that active ingredients 74, 89, 94 and 116, applied as 0.05wt% spray liquors, have a better fungicidal action (97%) than prior art active ingredient A (60%).
Claims (5)
1. A process for preparing a 1-halo-1-azolylethane derivative of the formula ##STR14## where R1 and R2 are C1 -C8 -alkyl, phenyl, biphenyl, naphthyl, benzyl C3 -C8 -cycloalkyl or C3 -C8 -cycloalkenyl, each of which is unsubstituted or substituted by halogen, nitro, phenoxy, alkyl, alkoxy, amino or haloalkyl, each of 1 to 4 carbon atoms,
n is an integer from 1 to 5, or 0,
E is Cl or Br, and
X is CH or N,
wherein a compound of the formula: ##STR15## wherein R1, R2 and n have the above meanings, is reacted with a compound of the formula: ##STR16## where X has the above meanings, in the presence of a thionyl halide of the formula SOE2, where E is Cl or Br.
2. The process as set forth in claim 1, where R1 is phenyl, R2 is methyl, E is chlorine, X is N and n is 0.
3. The process as set forth in claim 1, where R1 is 4-fluorophenyl, R2 is 2-fluorophenyl, E is chlorine, X is CH and n is 0.
4. The process as set forth in claim 1, where R1 is 2,4-dichlorophenyl, R2 is methyl, E is chlorine, X is CH and n is 1.
5. The process as set forth in claim 1, where R1 is 2,4-dichlorophenyl, R2 is methyl, E is chlorine, X is CH and n is 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3819903A DE3819903A1 (en) | 1988-06-11 | 1988-06-11 | 1-HALOGEN-1-AZOLYL-ETHAN DERIVATIVES AND FUNGICIDES CONTAINING THEM |
| DE3819903 | 1988-06-11 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07363773 Division | 1989-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5039815A true US5039815A (en) | 1991-08-13 |
Family
ID=6356333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/564,783 Expired - Fee Related US5039815A (en) | 1988-06-11 | 1990-08-09 | 1-halo-azolylethane derivatives and fungicides containing them |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5039815A (en) |
| EP (1) | EP0346727A1 (en) |
| JP (1) | JPH0232060A (en) |
| KR (1) | KR900000345A (en) |
| AR (1) | AR244670A1 (en) |
| AU (1) | AU615074B2 (en) |
| DE (1) | DE3819903A1 (en) |
| IL (1) | IL90530A0 (en) |
| NZ (1) | NZ229485A (en) |
| ZA (1) | ZA894374B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164408A (en) * | 1989-07-13 | 1992-11-17 | Basf Aktiengesellschaft | 1,2-dihaloazolylethane derivatives and crop protection agents containing them |
| US5358939A (en) * | 1992-06-25 | 1994-10-25 | Rohm And Haas Company | Fungicidal 2-aryl-2,2-disubstituted ethyl-1,2,4-triazoles |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3825586A1 (en) * | 1988-07-28 | 1990-02-01 | Basf Ag | SUBSTITUTED IMIDAZOLYL METHYLOXIRANES AND SUBSTITUTED IMIDAZOLYL PROPENES, THEIR PRODUCTION AND THEIR FUNGICIDES CONTAINING THEM |
| DE4009594A1 (en) * | 1990-03-26 | 1991-10-02 | Basf Ag | FUNGICIDAL AZOLYLETHANE DERIVATIVES |
| DE4034352A1 (en) * | 1990-10-29 | 1992-04-30 | Basf Ag | 1-HALOGEN-1-AZOLYLMETHANE DERIVATIVES AND FUNGICIDES CONTAINING THEM |
| TW210334B (en) * | 1990-12-12 | 1993-08-01 | Ciba Geigy Ag |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507140A (en) * | 1980-11-19 | 1985-03-26 | Imperial Chemical Industries Plc | Triazole and imidazole compounds useful as fungicides and plant growth regulators |
| US4657921A (en) * | 1984-05-23 | 1987-04-14 | Ciba-Geigy Corporation | 2,2-diphenyl-1-fluoro-1-azolylethanemicrobicides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3700916A1 (en) * | 1987-01-14 | 1988-07-28 | Bayer Ag | HALOGENALKYL, ALKENYL AND ALKINYL AZOLES |
-
1988
- 1988-06-11 DE DE3819903A patent/DE3819903A1/en not_active Withdrawn
-
1989
- 1989-05-31 AR AR89314049A patent/AR244670A1/en active
- 1989-06-05 IL IL90530A patent/IL90530A0/en unknown
- 1989-06-06 EP EP89110189A patent/EP0346727A1/en not_active Withdrawn
- 1989-06-09 ZA ZA894374A patent/ZA894374B/en unknown
- 1989-06-09 AU AU36201/89A patent/AU615074B2/en not_active Ceased
- 1989-06-09 NZ NZ229485A patent/NZ229485A/en unknown
- 1989-06-10 KR KR1019890008065A patent/KR900000345A/en not_active Application Discontinuation
- 1989-06-12 JP JP1146920A patent/JPH0232060A/en active Pending
-
1990
- 1990-08-09 US US07/564,783 patent/US5039815A/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507140A (en) * | 1980-11-19 | 1985-03-26 | Imperial Chemical Industries Plc | Triazole and imidazole compounds useful as fungicides and plant growth regulators |
| US4657921A (en) * | 1984-05-23 | 1987-04-14 | Ciba-Geigy Corporation | 2,2-diphenyl-1-fluoro-1-azolylethanemicrobicides |
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| Title |
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| Bergamann et al., "W-Fluoracetophenone. III, etc", JACS, 79, p. 4178 (1957). |
| Bergamann et al., W Fluoracetophenone. III, etc , JACS, 79, p. 4178 (1957). * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5164408A (en) * | 1989-07-13 | 1992-11-17 | Basf Aktiengesellschaft | 1,2-dihaloazolylethane derivatives and crop protection agents containing them |
| US5358939A (en) * | 1992-06-25 | 1994-10-25 | Rohm And Haas Company | Fungicidal 2-aryl-2,2-disubstituted ethyl-1,2,4-triazoles |
| US5462931A (en) * | 1992-06-25 | 1995-10-31 | Rohm And Haas Company | Fungicidal 2-heterocyclic-2,2-disubstituted-ethyl 1,2,4-triazoles |
| US5624916A (en) * | 1992-06-25 | 1997-04-29 | Rohm And Haas Company | Fungicidal 1,2,4-triazoles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3819903A1 (en) | 1989-12-21 |
| IL90530A0 (en) | 1990-01-18 |
| AR244670A1 (en) | 1993-11-30 |
| EP0346727A1 (en) | 1989-12-20 |
| JPH0232060A (en) | 1990-02-01 |
| NZ229485A (en) | 1990-10-26 |
| ZA894374B (en) | 1991-02-27 |
| AU3620189A (en) | 1989-12-14 |
| KR900000345A (en) | 1990-01-30 |
| AU615074B2 (en) | 1991-09-19 |
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